Process for the manufacture of phosphoric acid esters and phosphonic acid esters

ABSTRACT

WHEREIN R5 represents a C1-C4-alkyl radical together with bromotrichloromethane and a compound R-OH. R represents any aliphatic, araliphatic or aromatic radical or the radical of an enolised compound or R-OH represents an optionally substituted oximino compound or hydroxylamine.   WHEREIN R3 and R4 represent identical or different C1-C4 alkyl radicals and X represents an oxygen atom or the direct P-R3 bond, can be manufactured under mild conditions by reacting   Phosphoric or phosphonic acid esters of the formula

,llnited States Patent [1 1 Martin et a1.

1 1 PROCESS FOR THE MANUFACTURE OF PHOSPHORIC ACllD ESTERS AND PHOSPHONIC ACID ESTERS [76] Inventors: Henry Martin; Jozef Drabek, both of Basel, Switzerland [22] Filed: Apr. 1, 1970 [21] Appl. N0.: 24,853

[30] Foreign Application Priority Data Apr. 2, 1969 Switzerland 5106/69 [56] References Cited UNITED STATES PATENTS 6/1965 Mukaiyama et a1... 260/982 X 9/1967 Baranauckas et a1 260/985 OTHER PUBLICATIONS Houben-Weyl, Methoden Der Organischen Chemie, Vol. 12/2, Georg Thieme Verlag, (Stuttgart) 1964, page 335.

Kosolapoff, Organophosphorus Compounds, John Wiley & Sons, Inc. (New York) 1950, page 227.

[ Dec. 31, 1974 Primary Eraminer-Lorraine A. Weinberger Assistant Examiner-Richard L. Raymond Attorney, Agent, or Firm-Frederick H. Rabin; Harry Falber; Harry Goldsmith [57] ABSTRACT Phosphoric or phosphonic'acid esters of the formula wherein R and R represent identical or different C,C alkyl radicals and X represents an oxygen atom or the direct PR bond, can be manufactured under mild conditions by reacting wherein R represents a C,C -alkyl radical together with bromotrichloromethane and a compound ROH. R represents any aliphatic, araliphatic or aromatic radical or the radical of an enolised compound or R-OH represents an optionally substituted oximino compound or hydroxylamine.

6 Claims, No Drawings PROCESS FOR THE MANUFACTURE OF PHOSPHORIC ACID ESTERS AND PHOSPHONIC ACID ESTERS The present invention provides a process for the manufacture of phosphoric acid esters and phosphonic acid esters of the formula wherein R and R represent identical or different C,C alkyl radicals and X represents an oxygen atom or the direct PR 'bond, wherein a compound of the formula R-OH -or the radical in which one of the radicals R or R can be a hydrogen atom or the group -N (R6)(R1), wherein 'R represents a hydrogen atom or a C -C alkyl group and R reprewherein R represents a C,C -alkyl radical.

In the course of the reaction, CHCl and R Br are produced together with the desired compounds of formula I.

Trichlorobromomethane may be used as a solvent or as a diluent. In accordance with the end products produced, it is preferably employed in atleast stoichiometrically equivalent amounts relative to the two other reagents. ln this case another solvent or diluent which is free of hydroxyl groups is used for the reaction, where desired.

Possible substances which may be used as solvents are preferably hydrocarbons, for example, benzene, toluene, xylene, nitrobenzene, chlorobenzene, cyclohexane, n-pentane, n-hexane and petroleum ether mixtures, and also, for example, chloroform, bromoform, methylene chloride, ether, dioxan, tetrahydrofuran, acetonitrile and ethylene glycol dialkyl ethers.

Ketones can be used, provided they do not show any enolisation tendency which interferes with the course of the reaction.

Carbon tetrachloride may also be employed as the solvent. Admittedly it resembles trichlorobromomethane in its mode of action, but its reaction velocity constant k of splitting off a Cl from CCl is significantly smaller than the reaction velocity constant k of splitting off the Br from CCl Br. CCL, requires very much greater decomposition energies tostart the reaction according to the invention and therefore results in poor yields in the manufacture of compounds of formula'l. Under the conditions here mentioned, of a mild reaction of trichlorobromomethane, R-OH and R X- P(OR.,)(OR it can serve as an almost inert solvent or diluent.

The process of the present invention is advantageously carriedout at a reaction temperature within the range of-from 0 to l00C, preferably 15 to 50C.

R can be substituted by a variety of substituents, for example by one or more halogen atoms, nitro groups, aliphatic radicals including also CF carbalkoxy, carboxyamido, sulphonyl and amino groups. Fundamentally, however, the substituents should not have a determining effect on the course of the reaction.

The process of the present invention provides a means of manufacturing, in a simple manner, phosphoric acid esters and phosphonic acid esters which were hitherto obtained in an involved manner from the phosphoric acid ester halides or phosphoric acid ester halides respectively and the compounds of formula ROH, in the presence of an agent which binds hydrogen halide.

New and known phosphoric acid esters and phosphonic acid esters having a pesticidal action can be manufactured according to the new process.

The following Examples illustrate the invention:

EXAMPLE I The volatile constituents were distilled off and the 1 residue was kept for one hour at C/0.02 mm Hg.

50 g of a yellowish oil were left (yield: of theory), n 1.5120; boiling point 108 to ll5C/0.0l mm Hg.

The product has the following composition:

For CIQHIZCIQO4PI calculated found P I 9.29 9.3 7: Cl 3l.89 32.0.

Other phenylphosphates can be manufactured in the same manner as described in Example 1, for example 0,0-Dimethyl-O-(2,4,5-trichlorophenyl)-phosphate boiling point to l22C/0.l mm Hg 0,0-Dimethyl-O-(2,5 dichlor-4-iodophenyl)- phosphate melting point 58 to 59C 3 0.0-Diethyl-O-(2,5-dichloro-4-iodophenyl)- phosphate boiling point 138 to 140C/0.001 mm Hg 0,0-Dimethyl-O-(2,5-dichloro-4-bromophenyl)- phosphate melting point 64C 0,0-Diethyl-O-(2,5-dichloro-4-bromophenyl)- phosphate 11,, 1.5249 0,0-Diethyl-O-(4-nitrophenyl)-phosphate boiling point 1l8C/0.1 mm Hg 0,0-Dimethyl-O-(2,4-dichlorophenyl)-phosphate 0,0-Dimethyl-O-(2-chloro-4-tert.butylphenyl)- phosphate 0,0-Diethyl-O-(2,4,6-trichlorophenyl)-phosphate 0,0-Dimethyl-O-(4-cyanophenyl)-phosphate 0,0-Dimethyl-O-(3-methyl-4-methylmercaptophenyl)-phosphate boiling point 110C 0.001 mm Hg 0,0-Dimethyl-O-(4-trifluoromethylphenyl)-phosphate 0,0-Dimethyl-O-(3-chloro-4-trifluoromethylphenyl)- phosphate and 0,0-Dimethyl-O-(3 -trifluoromethyl-4-chlorophenyl)- phosphate.

lf in place of 0,0,0-trialkylphosphite alkyl-0,0- dialkylphosphite (with any desired C -C -alkyl radicals) is used, the corresponding phenylphosphonates are obtained, for example methyl-O-methyl-O-(2,5- dichlor-4-iodophenyl)-phosphate, ethyl-O-methyl-O- (2,5-dichlor-4-iodophenyl)-phosphate and ethyl-O- ethy1-O-(4-nitrophenyl)-phosphate.

Phenylphosph(on)ates of less simple structure are also obtainable without difficulties in the same manner, for example 0,0-Diethyl-(benzoxazol-Z-yl)-phosphate 33.3 g of triethylphosphite were added dropwise during 50 minutes. whilst stirring. to a suspension of 27.2 g of benzoxazolone in 40 cc of bromotrichloromethane. The temperature was kept at to C by cooling. After the end of the dropwise addition, the reaction mixture was stirred for a further hour.

The volatile constituents were distilled off and the residue was kept for one hour at 70C/0.02 mm Hg. 53 g (97.5 7( of theory) of a brown-reddish oil were left. n 1.5090

The product has the following composition:

For C H N0 calculated found P l 1.42 l 1.4 "/z N 5.16 5.3.

Any desired phosph(on)ates with heterocyclic substituents can be manufactured in a similar manner to that described in Example 2, for example N\ |L ]-o1 0011:):

EXAMPLE 3 The crude product was distilled over on a molecular distillation apparatus.

The product boils at C/0.04 mm Hg and has n,,- 1.4355.

The distilled product has the following composition:

For C;H NO P calculated found Any desired other oximephosphates are obtainable in a similar manner to that described in Example 3, for example Diethylphosphoryl-a-oximino-phenylacetonitrile 16.6 g of triethylphosphite were run into a suspension of 14.6 g of a-cyanobenzaldoxime in'5 0 cc of BrCC1 during minutes, whilst stirring. The temperature was kept below C by cooling. The reaction mixture was then stirred for a further hour at room temperature.

The volatile constituents were pre-distilled and the crude product was kept for 1 hour at C/0.02 mm Hg.

28.5 g of a yellowish oil were left; n 1.5149.

The product has the formula Analysis for C H N 0 p calculated found The following oximephosph(on)ates can also be manufactured in a similar manner to that described in Example 4:

EXAMPLE 5 lfequimolecular amounts of trimethylphosphite, trichlorobromomethane and acetoacetic acid dimethylamide are reacted in accordance with the manner'indicated in the preceding Examples, the compound of formula Boiling point 130 (molecular distillation) is obtained. Other phosph(on- )ates derived from aliphatic esters .or acid amides can also be manufactured in a similar manner, for example C. /0.8 mm. Hg.

Boiling point 92 C./0.02 mm. Hg.

55 I OCHs We claim:

1. A process for preparing phosphoric acid esters of C./0.001 mm. Hg.

in which R, represents C -C alkyl, phenyl or phenyl substituted by halogen or nitro, and R represents hydrogen, phenyl, alkylamino, dialkylamino or cyano; a heterocyclic residue containing 5 or 6 ring members and having optionally one or two benzene rings fused thereon. which residue may be substituted by alkyl or halogen: or the radical of an enolised aliphatic keto compound of the formula ell-R6 wherein one of R and R represents alkyl, carbalkoxy or carboxamide and the other represents carbalkoxy or carboxamide, which process comprises reacting (l) a phosphorus compound of the formula wherein R represents C C. alkyl, with (2) trichlorobromomethane and (3) a compound of the formula 2. A process according to claim 1 in which R represents the radical of an enolised aliphatic keto compound of the formula wherein one of R and R represents alkyl, carhalkoxy or carbm'rnnide and the other represents carhalknxy m carboxamide.

3. A process according to claim I, wherein trichlorobromomethane is employed in at least stoichiometrically equivalent amounts relative to each of the other two reagents.

4. A process according to claim 1, wherein the reaction is carried out in the presence of one or more solvents which are free of hydroxyl groups.

5. A process according to claim 1, wherein the reaction is carried out at a temperature within the range of from 0 to C.

6. A process according to claim 5, wherein the reaction is carried out at a temperature within the range of from 15 to 50C.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,857,907 7 Dated December 31, 1974 Inventor(s) Henry Martin and Jozef Drabek It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The following should appear in the heading:

Assignee: CIBA-GEIGY AG, Basel, Switzerland Signed and sealed this 1st day of April 1975.

(sat-TL) fittest: C. PTARSHALL DANN RUTH C. W150i? Commissioner of Patents attesting ilfficer and Trademarks FORM PO-105O (10-69) USCOMM'DC 603764 69 h ".5. GDVIRNIENT PRINTING OFFICI 1 I!" O3Sll, 

1. A PROCESS FOR PREPARING PHOSPHORIC ACID ESTERS OF THE FORMULA
 2. A process according to claim 1 in which R represents the radical of an enolised aliphatic keto compound of the formula
 3. A process according to claim 1, wherein trichlorobromomethane is employed in at least stoichiometrically equivalent amounts relative to each of the other two reagents.
 4. A process according to claim 1, wherein the reaction is carried out in the presence of one or more solvents which are free of hydroxyl groups.
 5. A process according to claim 1, wherein the reaction is carried out at a temperature within the range of from 0* to 100*C.
 6. A process according to claim 5, wherein the reaction is carried out at a temperature within the range of from 15* to 50*C. 